In order to obtain Al–Al2O3–ZrO2 composite refractories with excellent oxidation resistance, erosion resistance and thermal shock stability, metallic aluminium and fused Al2O3–ZrO2 were used as the raw materials, while phenolic resin was used as the binding agent. The microstructure was characterised by means of X-ray diffraction and scanning electron microscopy tests. Based on the reaction between zirconia and metallic aluminium under N2 flowing at 1300 °C, the reaction mechanism of zirconia and metallic aluminium in-situ reaction at 1300 °C to generate (Al2OC)x(AlN)1−x solid solution, zirconium nitride, and aluminium–zirconium alloy was revealed, and a model for the evolution of the phases in the aluminium-added Al–Al2O3–ZrO2 specimen was constructed to realise the Al–Al2O3–ZrO2 composite refractories phase controlling. Based on the good corrosion resistance of ZrO2 to CaO and the excellent results of the in-situ reaction of metallic aluminium to generate a large number of non-oxide reinforcing phases capable of replacing elemental C, this work is of great significance for the study of refractory in erosion-heavy environments, such as calcium-treated steel.
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